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Catalytic effect of thermal polyanhydro-alpha- amino acids on hydrolysis of p-nitrophenylacetate, noting role of histidine residues
Catalytic activity of thermal polyanhydro-alpha- amino acids for hydrolysis of rho-nitrophenyl acetate - catalysis by thermal polyamino acids
This paper describes the effect of surface catalysis on the heat transfer rate to the heat shield of a typical Transatmospheric Vehicle (TAV) during ascent and atmospheric entry. Surface kinetics and optical properties obtained from arc-jet tests on candidate thermal protection systems (coated metals) were used in a reacting boundary layer code to estimate the heating distribution along the surface of a TAV. Thermochemical stability of the coatings is described in terms of reduction in emittance and loss of opacifiers from the coatings during the arc-jet tests.
Experimental results on the problem of reducing aerodynamic heating on space shuttle orbiter surfaces are presented. Data include: (1) development of a laboratory flow reactor technique for measuring gamma sub O and gamma sub N on candidate materials at surfaces, T sub w, in the nominal range 1000 to 2000, (2) measurements of gamma sub O and gamma sub N above 1000 K for both the glass coating of a reusable surface insulation material and the siliconized surface of a reinforced pyrolyzed plastic material, (3) measurement of the ablation behavior of the coated RPP material at T sub w is greater than or equal to 2150 K, (4) X-ray photoelectron spectral studies of the chemical constituents on these surfaces before and after dissociated gas exposure, (5) scanning electron micrograph examination of as-received and reacted specimens, and (6) development and exploitation of a method of predicting the aerodynamic heating consquences of these gamma sub O(T sub w) and gamma sub N(T sub w) measurements for critical locations on a radiation cooled orbiter vehicle.
Titanium aluminides and titanium alloys are candidate materials for use in hot structure and heat-shield components of hypersonic vehicles because of their good strength-to-weight characteristics at elevated temperature. However, in order to utilize their maximum temperature capability, they must be coated to resist oxidation and to have a high total remittance. Also, surface catalysis for recombination of dissociated species in the aerodynamic boundary layer must be minimized. Very thin chemical vapor deposition (CVD) coatings are attractive candidates for this application because of durability and very light weight. To demonstrate this concept, coatings of boron-silicon and aluminum-boron-silicon compositions were applied to the titanium-aluminides alpha2 (Ti-14Al-21Nb), super-alpha2 (Ti-14Al-23-Nb-2V), and gamma (Ti-33Al-6Nb-1Ta) and to the titanium alloy beta-21S (Ti-15Mo-3Al-3Nb-0.2Si). Coated specimens of each alloy were subjected to a set of simulated hypersonic vehicle environmental tests to determine their properties of oxidation resistance, surface catalysis, radiative emittance, and thermal shock resistance. Surface catalysis results should be viewed as relative performance only of the several coating-alloy combinations tested under the specific environmental conditions of the LaRC Hypersonic Materials Environmental Test System (HYMETS) arc-plasma-heated hypersonic wind tunnel. Tests were also conducted to evaluate the hydrogen transport properties of the coatings and any effects of the coating processing itself on fatigue life of the base alloys. Results are presented for three types of coatings, which are as follows: (1) a single layer boron silicon coating, (2) a single layer aluminum-boron-silicon coating, and (3) a multilayer coating consisting of an aluminum-boron-silicon sublayer with a boron-silicon outer layer.
Aerothermodynamic development flight test data from the first orbital flight test of the Space Transportation System (STS) transmitted after entry blackout is given. Engineering predictions of boundary layer transition and numerical simulations of the orbiter flow field were confirmed. The data tended to substantiate preflight predictions of surface catalysis phenomena. The thermal response of the thermal protection system was as expected. The only exception is that internal free convection was found to be significant in limiting the peak temperature of the structure in areas which do not have internal insulation.
This paper presents results of flowfield calculations for typical hypersonic reentry conditions encountered by the nose region of the Space Shuttle Orbiter. Most of the transitional flow regime is covered by the altitude range of 150 to 92 km. Calculations were made with the Direct Simulation Monte Carlo (DSMC) method that accounts for translational, rotational, vibrational, and chemical nonequilibrium effects. Comparison of the DSMC heating results with both Shuttle flight data and continuum predictions showed good agreement at the lowest altitude considered. However, as the altitude increased, the continuum predictions, which did not include slip effects, departed rapidly from the DSMC results by overpredicting both heating and drag. The results demonstrate the effects of rarefaction on the shock and the shock layer, along with the extent of the slip and temperature jump at the surface. Also, the sensitivity of the flow structure to the gas-surface interaction model, thermal accommodation, and surface catalysis are studied.
Aerogels, mesoporous materials with extreme material properties including high specific surface area, low density, and low thermal conductivity, can be useful for applications including catalysis, sorption media, and drug delivery. The low thermal conductivity and high surface area of aerogels makes them advantageous as thermal management systems, specifically for aerospace or aeronautics applications. However, the pore collapse and subsequent surface area decrease of aerogels following exposure to high temperatures must be mitigated to allow aerogels to be effectively used in thermal management applications. This work investigates the anionic surfactant sodium dodecyl sulfate (SDS) and the nonionic surfactant Pluronic® P-123 as surfactant templates in yttria-stabilized zirconia (YSZ) aerogels. By utilizing surfactant templates, known to influence pore structure, it is anticipated that sintering and densification of the aerogels following high-temperature exposure will be mitigated. It was determined that the addition of SDS and P-123 increased the surface area and pore volume of as-dried aerogels and suppressed crystallite growth at high temperatures. However, the impact of surfactant templates on the surface area and pore volume of heat-treated aerogels was negligible, potentially due to low concentrations of surfactant and the removal of the surfactant following high-temperature exposure.
The Hypersonic Inflatable Aerodynamic Decelerators (HIAD) project has invested in development of multiple thermal protection system (TPS) candidates to be used in inflatable, high downmass, technology flight projects. Flexible TPS is one element of the HIAD project which is tasked with the research and development of the technology ranging from direct ground tests, modelling and simulation, characterization of TPS systems, manufacturing and handling, and standards and policy definition. The intent of flexible TPS is to enable large deployable aeroshell technologies, which increase the drag performance while significantly reducing the ballistic coefficient of high-mass entry vehicles. A HIAD requires a flexible TPS capable of surviving aerothermal loads, and durable enough to survive the rigors of construction, handling, high density packing, long duration exposure to extrinsic, in-situ environments, and deployment. This paper provides a comprehensive overview of key work being performed within the Flexible TPS element of the HIAD project. Included in this paper is an overview of, and results from, each Flexible TPS research and development activity, which includes ground testing, physics-based thermal modelling, age testing, margins policy, catalysis, materials characterization, and recent developments with new TPS materials.
The droplet emulsion technique is presently used to examine the undercooling and crystallization behavior of pure antimony. Control of droplet size and applied cooling rate allowed maximum undercooling to be extended from 0.08 to 0.23 T(m). A droplet coating was produced by means of emulsification which appears to furnish a favorable crystallographic matching for effective nucleation catalysis of a metastable simple cubic structure. Thermal analysis shows the melting temperature of the single cubic phase to be about 625 C.
Many of the current direct simulation Monte Carlo (DSMC) codes still employ only simple surface catalysis models. These include only basic mechanisms such as dissociation, recombination, and exchange reactions, without any provision for adsorption and finite rate kinetics. Incorporating finite rate chemistry at the surface is increasingly becoming a necessity for various applications such as high speed re-entry flows over thermal protection systems (TPS), micro-electro-mechanical systems (MEMS), surface catalysis, etc. In the recent years, relatively few works have examined finite-rate surface reaction modeling using the DSMC method.In this work, a generalized finite-rate surface chemistry framework incorporating a comprehensive list of reaction mechanisms is developed and implemented into the DSMC solver SPARTA. The various mechanisms include adsorption, desorption, Langmuir-Hinshelwood (LH), Eley-Rideal (ER), Collision Induced (CI), condensation, sublimation, etc. The approach is to stochastically model the various competing reactions occurring on a set of active sites. Both gas-surface (e.g., ER, CI) and pure-surface (e.g., LH, desorption) reaction mechanisms are incorporated. The reaction mechanisms could also be catalytic or surface altering based on the participation of the bulk-phase species (e.g., bulk carbon atoms). Marschall and MacLean developed a general formulation in which multiple phases and surface sites are used and we adopt a similar convention in the current work. Microscopic parameters of reaction probabilities (for gas-surface reactions) and frequencies (for pure-surface reactions) that are require for DSMC are computed from the surface properties and macroscopic parameters such as rate constants, sticking coefficients, etc. The energy and angular distributions of the products are decided based on the reaction type and input parameters. Thus, the user has the capability to model various surface reactions via user-specified reaction rate constants, surface properties and parameters.
This paper describes arc-jet data obtained on the performance of glass coated thermal protection systems in a convectively heated environment. These data confirm earlier flight and arc-jet data that show an increased surface catalysis with salt contamination and a decreased surface catalysis near the softening point temperature of the glass. In addition, surface temperature distributions along sphere-cones with abruptly changing surface catalysis were measured near the stagnation point and compared well with computations using a reacting boundary layer code.
Alternate methods of generating hydrogen from the sulfuric acid thermal or electrochemical cycles are presented. A number of processes requiring chemical, electrochemical or photochemical methods are also presented. These include the design of potential photoelectrodes and photocatalytic membranes using Ru impregnated nafion tubing, and the design of experiments to study the catalyzed electrolytic formation of hydrogen and sulfuric acid from sulfur dioxide and water using quinones as catalysts. Experiments are carried out to determine the value of these approaches to energy conversion.
The thermal-control requirements for design-optimized aeromaneuvering performance are determined for space-based applications and low-earth orbit sorties involving large, multiple plane-inclination changes. The leading-edge heating analysis is the most advanced developed for hypersonic-rarefied flow over lifting surfaces at incidence. The effects of leading-edge bluntness, low-density viscous phenomena, and finite-rate flow-field chemistry and surface catalysis are accounted for. The predicted aerothermodynamic heating characteristics are correlated with thermal-control and flight-performance capabilities. The mission payload capability for delivery, retrieval, and combined operations is determined for round-trip sorties extending to polar orbits. Recommendations are given for future design refinements. The results help to identify technology issues required to develop prototype operational systems.
The fundamental processes occurring during the thermal and oxidative degradation of hydrocarbons are reviewed. Particular emphasis is given to various classes of liquid lubricants such as mineral oils, esters, polyphenyl ethers, C-ethers, and fluorinated polyethers. Experimental techniques for determining thermal and oxidative stabilities of lubricants are discussed. The role of inhibitors and catalysis is also covered.
The fundamental processes which occur during the thermal and oxidation degradation of hydrocarbons is reviewed. Various classes of liquid lubricants such as mineral oils, esters, polyphenyl ethers, C-ethers, and fluorinated polyethers are emphasized. Techniques to determine thermal and oxidative stabilities of lubricants are discussed. The role of inhibitors and catalysis is examined.
Systems requirements for design-optimized, lateral-turn performance were determined for reusable, space-based applications and low-Earth orbits involving large multiple plane-inclination changes. The aerothermodynamic analysis is the most advanced available for rarefield-hypersonic flow over lifting surfaces at incidence. The effects of leading-edge bluntness, low-density viscous phenomena, and finite-rate flow-field chemistry and surface catalysis are accounted for. The predicted aerothermal heating characteristics are correlated with thermal-control and flight-performance capabilities. The mission payload capacity for delivery, retrieval, and combined operations was determined for round-trip sorties extending to polar orbits. Recommendations are given for future design refinements. The results help to identify technology issues required to develop prototype operational vehicles.
Systems requirements for design-optimized, lateral-turn performance were determined for reusable, space-based applications and low-earth orbits involving large multiple plane-inclination changes. The aerothermodynamic analysis is the most advanced available for rarefied-hypersonic flow over lifting surfaces at incidence. The effects of leading-edge bluntness, low-density viscous phenomena, and finite-rate flow-field chemistry and surface catalysis are accounted for. The predicted aerothermal heating characteristics are correlated with thermal-control and flight-performance capabilities. The mission payload capacity for delivery, retrieval, and combined operations was determined for round-trip sorties extending to polar orbits. Recommendations are given for future design refinements. The results help to identify technology issues required to develop prototype operational vehicles.